The Mexico City Metropolitan Area (MCMA) is one of the largest cities in the world, and as with many megacities worldwide, it experiences serious air quality and pollution problems, especially with ozone and particulate matter. Ozone levels exceed the health-based standard, which is equivalent to the U.S. standard, on approximately 80% of all days, and concentrations of particulate matter 10 μm and smaller (PM10) exceed the standard on more than 40% of all days in most years. Particulate polycyclic aromatic hydrocarbons (PAHs) are a class of semi-volatile compounds that are formed during combustion and many of these compounds are known or suspected carcinogens. Recent studies on PAHs in Mexico City indicate that very high concentrations have been observed there and may pose a serious health hazard.

The first part of this thesis describes results from the Megacities Initiative: Local and Regional Observations (MILAGRO) study in Mexico City in March 2006. During this field campaign, we measured PAH and aerosol active surface area (AS) concentrations at six different locations throughout the city using the Aerodyne Mobile Laboratory (AML). The different sites encompassed a mix of residential, commercial, industrial, and undeveloped land use. The goals of this research were to describe spatial and temporal patterns in PAH and AS concentrations, to gain insight into sources of PAHs, and to quantify the relationships between PAHs and other pollutants. We observed that the highest measurements were generally found at sites with dense traffic networks. Also, PAH concentrations varied considerably in space. An important implication of this result is that for risk assessment studies, a single monitoring site will not adequately represent an individual's exposure.

Source identification and apportionment are essential for developing effective control strategies to improve air quality and therefore reduce the health impacts associated with fine particulate matter and PAHs. However, very few studies have separated gasoline- versus diesel-powered vehicle emissions under a variety of on-road driving conditions. The second part of this thesis focuses on distinguishing between the two types of engine emissions within the MCMA using positive matrix factorization (PMF) receptor modeling. The Aerodyne Mobile Laboratory drove throughout the MCMA in March 2006 and measured on-road concentrations of a large suite of gaseous and particulate pollutants, including carbon dioxide, carbon monoxide (CO), nitric oxide (NO), benzene (C6H6), formaldehyde (HCHO), ammonia (NH3), fine particulate matter (PM2.5), PAHs, and black carbon (BC). These pollutant species served as the input data for the receptor model. Fuel-based emission factors and annual emissions within Mexico City were then calculated from the source profiles of the PMF model and fuel sales data. We found that gasoline-powered vehicles were responsible for 90% of mobile source CO emissions and 85% of VOCs, while diesel-powered vehicles accounted for almost all of NO emissions (99.98%). Furthermore, the annual emissions estimates for CO and VOC were lower than estimated during the MCMA-2003 field campaign.

The number of megacities is expected to grow dramatically in the coming decades. As one of the world's largest megacities, Mexico City serves as a model for studying air quality problems in highly populated, extremely polluted environments. The results of this work can be used by policy makers to improve air quality and reduce related health risks in Mexico City and other megacities.